“镉米”生物能源化过程中Cd的迁移途径

镉属于环境中持久性污染物,毒性大,对环境及人类造成严重危害,"镉米"事件已引起了对环境镉污染尤其是土壤镉污染的高度关注。利用镉米生产酒精不但能为企业能源生产提供新的原料来源,而且可解决有害大米的出路问题。通过摇瓶和UASB厌氧反应器实验,重点研究了Cd2+在厌氧处理过程中的迁移途径。结果表明,90%以上的Cd2+主要以微溶的形式富集于厌氧污泥里。厌氧泥离心分离:泥中镉浓度为0.35~0.40 mg/kg,水中镉浓度低于0.025 mg/kg。厌氧出水镉浓度在0.010~0.015 mg/kg,可以实现达标排放。出水VFA基本维持在300~500 mg/L,COD的去除率达65%~80%。实验结果可为镉米能源化利用提供一定的理论依据和技术支撑。     

Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.     

Residual metal concentrations in soils and leaf accumulations in tobacco a decade following farmland application of municipal sludge

The objectives of this investigation were to examine the long-term residual effects of metal loading through sewage sludge applications on the total vs. diethylene triamine pentacetic acid (DTPA) extractable metal concentrations in soil and leaf accumulations in tobacco. Maryland tobacco (Nicotiana tabacum L.), cv. 'MD 609', was grown in 1983 and 1984 at two sites in Maryland that had been amended in 1972 with dewatered, digested sewage sludge from washington, DC, at rates equal to 0, 56, 112 and 224 mg ha(-1). The metal concentrations in the sludge, in mg kg(-1) dry weight, were: 1300 Zn, 570 Cu, 280 Pb, 45 Ni and 13 Cd. Soil samples collected from the surface horizon and composite leaf samples of cured tobacco were analyzed for total Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations. The soil samples were also examined for soil pH and DTPA extractable metals. Equations were generated using polynomic and stepwise regression analyses which described the relationships between total vs. DTPA extractable soil metals, and between DTPA soil and soil pH vs. plant metal concentrations, respectively. Significant increases were observed for both total and DTPA extractable metal concentrations for all metals, with all but total Mn and Ni being significant for linear and quadratic effects regarding sludge rates. However, linear relationships were found between DTPA extractable vs. total soil concentrations for all elements except Pb and Ni which were quadratic. Significant increases in plant Zn, Cu, Mn, Ni and Cd and decreases in Fe were observed with increased sludge rates. Plant Pb levels were unaffected by sludge applied Pb. Linear relationships were observed between plant Zn and Cd and DTPA soil metal levels: however, Mn and Cu levels were described by quadratic and cubic relationship, respectively. Relationships between plant Fe and Pb and DTPA extractable concentrations were nonsignificant. Additional safeguards to protect crop contamination from heavy metals such as Cd were discussed.     

Speciation and mobility of cadmium in straw and wood combustion fly ash

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.     

Determination of chemical availability of cadmium and zinc in soils using inert soil moisture samplers

A rapid method for extracting soil solutions using porous plastic soil-moisture samplers was combined with a cation resin equilibration based speciation technique to look at the chemical availability of metals in soil. Industrially polluted, metal sulphate amended and sewage sludge treated soils were used in our study. Cadmium sulphate amended and industrially contaminated soils all had > 65% of the total soil solution Cd present as free Cd2+. However, increasing total soil Cd concentrations by adding CdSO4 resulted in smaller total soil solution Cd. Consequently, the free Cd2+ concentrations in soil solutions extracted from these soils were smaller than in the same soil contaminated by sewage sludge addition. Amendment with ZnSO4 gave much greater concentrations of free Zn2+ in soil solutions compared with the same soil after long-term Zn contamination via sewage sludge additions. Our results demonstrate the difficulty in comparing total soil solution and free metal ion concentrations for soils from different areas with different physiochemical properties and sources of contamination. However, when comparing the same Woburn soil, Cd was much less available as Cd2+ in soil solution from the CdSO4 amended soils compared with soil contaminated by about 36 years of sewage sludge additions. In contrast, much more Zn was available in soil solution as free Zn2+ in the ZnSO4 amended soils compared with the sewage sludge treated soils.     

Integrated assessment of heavy metal (Pb, Zn, Cd) highway pollution: bioaccumulation in soil, Graminaceae and land snails

To assess the contamination induced by traffic at the vicinity of a highway (A31, France), several complementary studies were carried out on two sites, with different profiles and traffic intensity. Concentrations of zinc, lead and cadmium were measured by atomic absorption spectrophotometry in deposits, roadside soil and autochthonous plants (Graminaceae) gathered at the vicinity of the highway (1-320 m), and in the viscera of snails Helix aspersa, transferred as sentinel in the sites. According to the results obtained for different compartments, the highway induces a contamination on the surrounding environment, up to 320 m, but with the maximum contamination observed between 5 and 20 m: the concentrations measured in plants at the vicinity of the highway were 2.1 mg Pb kg(-1) DW, 0.06 mg Cd kg(-1) DW, 62 mg Zn kg(-1) DW and the concentrations measured in snails were 21.3 mg Pb kg(-1) DW, 5.7 mg Cd kg(-1) DW, 510.8 mg Zn kg(-1) DW. The levels measured decreased with increasing distance from the highway. Results of the three metals studied indicated that lead seems to be the best metal to evaluate road transport contamination.     

Effects of sewage sludge amendment on heavy metal accumulation and consequent responses of Beta vulgaris plants

Use of sewage sludge, a biological residue produced from sewage treatment processes in agriculture is an alternative disposal technique of waste. To study the usefulness of sewage sludge amendment for palak (Beta vulgaris var. Allgreen H-1), a leafy vegetable and consequent heavy metal contamination, a pot experiment was conducted by mixing sewage sludge at 20% and 40% (w/w) amendment ratios to the agricultural soil. Soil pH decreased whereas electrical conductance, organic carbon, total N, available P and exchangeable Na, K and Ca increased in soil amended with sewage sludge in comparison to unamended soil. Sewage sludge amendment led to significant increase in Pb, Cr, Cd, Cu, Zn and Ni concentrations of soil. Cd concentration in soil was found above the Indian permissible limit in soil at both the amendment ratios.

The increased concentration of heavy metals in soil due to sewage sludge amendment led to increases in heavy metal uptake and shoot and root concentrations of Ni, Cd, Cu, Cr, Pb and Zn in plants as compared to those grown on unamended soil. Accumulation was more in roots than shoots for most of the heavy metals. Concentrations of Cd, Ni and Zn were more than the permissible limits of Indian standard in the edible portion of palak grown on different sewage sludge amendments ratios. Sewage sludge amendment in soil decreased root length, leaf area and root biomass of palak at both the amendment ratios, whereas shoot biomass and yield decreased significantly at 40% sludge amendment. Rate of photosynthesis, stomatal conductance and chlorophyll content decreased whereas lipid peroxidation, peroxidase activity and protein and proline contents, increased in plants grown in sewage sludge-amended soil as compared to those grown in unamended soil.

The study clearly shows that increase in heavy metal concentration in foliage of plants grown in sewage sludge-amended soil caused unfavorable changes in physiological and biochemical characteristics of plants leading to reductions in morphological characteristics, biomass accumulation and yield. The study concludes that sewage sludge amendment in soil for growing palak may not be a good option due to risk of contamination of Cd, Ni and Zn and also due to lowering of yield at higher mixing ratio.     

Influence of cadmium on carbon and nitrogen mineralization in sewage sludge amended soils

The effect of cadmium on C and N mineralization in sewage sludge amended and unamended sandy loam, loam and clay loam soils was studied during 2 months incubation at 30+/-1 degrees C. The sludge amendment caused 15-39% increase in microbial respiration, with the maximum C mineralization in sandy loam and the minimum in loam soil. The addition of 10 microg Cd g(-1) soil had no remarkable effect on C and N mineralization and microbial biomass; whereas significant decreases in the above parameters were observed at 25 and 50 microg Cd g(-1) soil, irrespective of the sludge addition. Less NO3(-)-N accumulated at higher Cd concentration. Cd recovery was high in sandy loam and low in clay loam soil. DTPA extractable Cd exhibited a significant negative correlation with microbial biomass (r=-0.58* to -0.86*; p < 0.05).     

The uptake of cadmium and zinc by the bird-cherry oat aphid Rhopalosiphum padi (Homoptera:Aphididae) feeding on wheat grown on sewage sludge amended agricultural soil

A greenhouse trial investigated the uptake of cadmium and zinc by the bird-cherry oat aphid (Rhopalosiphum padi) feeding on wheat grown on sewage sludge amended soil. The trial was conducted at application rates of 0, 5, 7.5, 10, 15 and 20 tonnes ha(-1) dry solids. Concentrations of Cd and Zn were within current UK limits for potentially toxic elements in soils amended with sewage sludge. Cd and Zn in wheat plants were significantly greater than controls. Batches of aphids feeding on the wheat also showed a significant increase in the uptake of Cd and Zn. This study demonstrates a potential route of exposure to Cd and Zn for the predators of cereal aphids.     

Cadmium (Cd) distribution and contamination in Chinese paddy soils on national scale

Rice is a staple food by an increasing number of people in China. As more issues have arisen in China due to rice contaminated by cadmium (Cd), Cd contamination in arable soils has become a severe problem. In China, many studies have examined Cd contamination in arable soils on a national scale, but little studies have focused on the distribution of Cd in paddy fields. This study explored the spatial pattern of Cd in paddy soils in China, made a preliminary evaluation of the potential risk, and identified the most critically contaminated regions based on the domestic rough rice trade flow. The results showed that Cd concentrations in paddy soils in China ranged from 0.01 to 5.50 mg/kg, with a median value of 0.23 mg/kg. On average, the highest Cd concentrations were in Hunan (0.73 mg/kg), Guangxi (0.70 mg/kg), and Sichuan (0.46 mg/kg) provinces. Cd concentrations in paddy soils in central and western regions were higher than those in eastern regions, especially the southeastern coastal regions. Of the administrative regions, Cd standard exceedance rate was 33.2 %, and the heavy pollution rate was 8.6 %. Regarding to Cd of paddy soil, soil environmental quality was better in Northeast China Plain than in Yangtze River Basin and southeastern coastal region. Mining activities were the main anthropogenic pollution source of Cd in Chinese paddy soil. Based on rice trade, more of the Chinese population would be exposed to Cd through intake of rice produced in Hunan province. Certain regions that output rice, especially Hunan province, should be given priority in the management and control of Cd contamination in paddy soil.     

Monitoring heavy metal concentrations in leachates from a forest soil subjected to repeated applications of sewage sludge

The aim of the study was to establish whether the repeated application of sewage sludge to an acid forest soil (Dystric Cambisol) would lead to short-term groundwater contamination. Sludge was applied at four loading rates (0, 2.4, 17 and 60 Mg ha⁻¹) in two consecutive years and leachates were analysed. Heavy metal inputs to soils at the lowest dose were below EC regulations but, at higher doses, limits for Zn, Cd, Cr and Ni were exceeded. Repeated application of sludge at 60 Mg ha⁻¹ resulted in significantly (P < 0.05) higher concentrations of Zn, Cd, Cr and Ni in the leachates than with other treatments. The drinking water standards for Cd and Ni were surpassed in all treatments. Control plots were contaminated by groundwater flow despite the existence of buffer zones between plots. This complicated interpretation of the results, highlighting the importance of careful design of this type of experiment.     

区域农田镉含量空间变异与综合风险的不确定性评估

我国小麦镉 (Cd) 污染格局多样,从不确定性角度评估区域小麦田Cd累积风险有助于提升污染防治决策的准确性。本研究基于不确定性理论,将蒙特卡洛 (Monte-Carlo) 随机模拟方法引入到区域土壤-小麦系统Cd污染综合风险评估中,结合多元统计和空间分析开展实例研究。结果表明河南省某小麦主产区92.8%的土壤样品Cd含量超过农田土壤风险筛选值 (0.6 mg·kg⁻¹) ,84.0%的小麦籽粒样品Cd含量超过国家食品安全限量标准 (0.1 mg·kg⁻¹) 。区域土壤-小麦系统Cd累积水平整体上呈现西北高东南低的空间分布格局。区域Cd生态风险以中度污染为主。区域人群Cd摄入量超过WHO推荐安全值的风险概率为31.6%,控制土壤Cd累积趋势可将该超标风险下降至7.3%。不确定性模拟、空间分析和场景分析的综合应用可准确识别农田Cd污染风险等级和相应概率,为区域Cd污染防治提供决策建议。     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg(-1)) and DEHP (100 mg kg(-1)) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1-0.45 μm to 500-2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

云南松华坝流域3种本土野生植物镉富集特性比较与应用

在镉(Cd)污染区域筛选富集能力强的本土野生植物是Cd污染土壤植物修复的路径之一。在云南松华坝流域土壤Cd含量超风险筛选值地块生长的杂草中,初步筛查表明牛膝菊、艾蒿和灰藜具有Cd富集潜力。为进一步探明其修复能力,通过盆栽和田间实验比较了这3种野生植物的Cd富集特性和修复能力。结果表明,牛膝菊和艾蒿Cd富集系数与转运系数均大于1,灰藜小于1。施肥措施不仅能显著提高3种本土野生植物的株高和地上部生物量,而且能显著提高牛膝菊地上部和根系的Cd含量、Cd转运系数和Cd富集系数。牛膝菊地上部和根系的Cd含量以及艾蒿的根系Cd含量均随土壤Cd含量的增加而增加。与艾蒿相比,牛膝菊具有更强的Cd转运和富集能力。在100 mg·kg⁻¹外源Cd添加的土壤中,牛膝菊的地上部和根系Cd含量分别为165.5 mg·kg⁻¹和147.5 mg·kg⁻¹。田间实验表明,每茬牛膝菊和艾蒿的鲜重分别为26.0 t·hm⁻²和32.0 t·hm⁻²,可分别带走Cd 3.29 g·hm⁻²和3.35 g·hm⁻²,均可用作当地土壤修复的备选植物。该结果可为相似环境下的土壤镉污染植物修复材料的选择提供参考。     

Cadmium contamination in orchard soils and fruit trees and its potential health risk in Guangzhou, China

This study examines cadmium (Cd) contamination in orchard soils and fruit trees in Guangzhou, China, and assesses its potential health risk. Soils and tissues samples of three species of fruit trees were collected from three orchards. The average soil Cd concentration was 1.27, 1.84 and 0.68 mg/kg in orchards I, II, and III, respectively. The carambola (Averrhoa carambola) accumulated exceptionally high concentrations of Cd (7.57, 10.84, 9.01 and 2.15 mg/kg dw in root, twig, leaf and fruit, respectively), being 6.0-24 times and 4.0-10 times the corresponding tissue Cd in the longan (Dimocarpus longan) and wampee (Clausena lansium), respectively. Furthermore, all Cd concentrations (0.04-0.25 mg Cd/kg fw) of the fruits exceeded the tolerance limit of cadmium in foods of PR China (0.03 mg/kg fw). Our results indicate that the carambola tree has high Cd accumulation capacity and might be a Cd accumulator; and its fruit, among the three species of fruits studied, also poses the highest potential health risk to local residents.     

山西省城市污泥农用潜力与安全施用

城市污泥中重金属的含量是限制污泥农用的主要泥质因素,本研究对山西省不同地区城市污泥采样分析结果表明,污泥pH为6.76~7.78、N+P2O5+K2O含量为3.03%~21.39%、有机质含量为18.5%~68.8%、重金属Cu、Zn、As、Hg、Pb、Cd和Cr含量分别为61.1~225.4、76.2~1 557.1、11.5~29.1、0.2~1.7、13.5~89、0.5~8.6和108.9~328.1 mg/kg,均符合农用泥质标准(CJ/T309-2009)中限定的泥质要求。依据山西省不同地区农田土壤重金属含量以及土壤环境质量二级标准,山西省不同地区土壤重金属环境容量大小顺序依次均为Pb> Zn> Cr> Cu> As> Hg> Cd。以年施入污泥量7 500 kg/(hm2·a) 计算,山西省晋北地区污泥连续施用年限为大同市约为117年,朔州市约为217年,忻州市约为133年,晋中地区太谷县约为6年,晋东南地区晋城市约为163年,长治市约为29年。     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 x 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre(-1), six plots were mixed with sewage sludge (SS) at 15 t acre(-1), and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO3, NH4, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO3-N and NH4-N) in runoff water than SS treatments. Total marketable yield (lbs acre(-1)) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

Cadmium effect on the structure of supra- and subpharyngeal ganglia and the neurosecretory processes in earthworm Dendrobaena veneta (Rosa)

Cadmium effects on the supra- and subpharyngeal ganglia, neurosecretion and RNA content in the neurosecretory cells were tested in earthworms Dendrobaena veneta exposed to 10 and 50 mg Cd kg(-1) in soil after 20 days of the experiment. Accumulation of cadmium in the ganglia of nervous system was also measured using AAS method. Cadmium was accumulated in the nervous system. The accumulated amount was proportional to Cd soil concentration and the exposure time. A considerable fall in neurosecretion and RNA content in the neurosecretory cells and neurosecretion in the neuropile (the axons) of both tested ganglia was induced by 50 mg Cd kg(-1). It seemed that neurosecretion synthesis and its axonal transport could be suppressed. Cadmium caused degenerative changes as vacuolization of the neurosecretory cells and neuropile in both tested ganglia.     

Cadmium effect on the ovarian structure in earthworm Dendrobaena veneta (Rosa)

Cadmium effects on the ovary structure and oocytes were tested in earthworms Dendrobaena veneta exposed to 10 and 50 mg Cd kg(-1) in soil after 10 and 20 days of the experiment. In both experimental doses cadmium caused damage to the structure of the ovary but the effects were different in each group. At 10 mg Cd kg(-1) concentration in soil, young stages of oocytes and trophocytes were most sensitive to cadmium deleterious effects whereas somatic cells in the ovarian stroma were only slightly affected. Cadmium. at a concentration of 50 mg Cd kg(-1) in soil caused most damage in the somatic cells leading to the occurrence of unnaturally swollen elements and desmosomes destruction. At both experimental concentrations cadmium induced degenerative changes in cell nuclei and an increase in number of cell organelles (RER and Golgi complex elements) in the cytoplasm of oocytes and trophocytes. These also proved to be more active. No ultrastructural changes were manifested in oogonia. In both experimental groups degenerative changes occurred as early as after 10 days of Cd exposure.